Hisato Iwata

Global contamination by persistent organochlorines and their ecotoxicological impact on marine mammals

The present paper overviews the global contamination by persistent organochlorines and their ecotoxicological implications on marine mammals. The recent pattern of contamination by organochlorine residues in the coastal environment is prominent in tropical regions due to continuous usage in the low-latitude developing countries. The major emission source of organochlorines is probably the tropical belt and large quantities of volatilized contaminants are dispersed through the atmosphere on global terms. Reflecting this, a considerable contamination was observed in open ocean tropical waters as well as in the Arctic and nearby waters. The study of the mass transfer of organochlorines at the air-water interface suggests that the oceanic water bodies, particularly Arctic waters, act as a sink for persistent contaminants. In this regard, the marine mammals, particularly cetaceans, are one of the animal groups receiving high concentrations of persistent organochlorines arising out of a worldwide contamination. They can amplify much greater amounts of toxic contaminants through feeding and also pass them in large quantities from one generation to the next through lactation. Unfortunately, these animals have a smaller capacity for degradation of these contaminants due to the specific mode of cytochrome P-450 enzyme systems. These drug-metabolizing enzyme systems may be related to the possible effects of persistent organochlorines, particularly coplanar PCBs. Furthermore, the residue levels of these contaminants in marine mammals are unlikely to decline in the near future. Considering all these facts, it may be concluded that marine mammals are one of the most vulnerable and possible target organisms with regard to long-term toxicity of hazardous man-made chemicals in the future.

Geographical distribution of persistent organochlorines in air, water and sediments from Asia and Oceania, and their implications for global redistribution from lower latitudes.

Persistent organochlorines in air, river water and sediment samples were analysed from eastern and southern Asia (India, Thailand, Vietnam, Malaysia, Indonesia) and Oceania (Papua New Guinea and Solomon Islands) to elucidate their geographical distribution in tropical environment. The concentrations of organochlorines in these abiotic samples collected from Taiwan, Japan and Australia were also monitored for comparison. Atmospheric and hydrospheric concentrations of HCHs (hexachlorocyclohexanes) and DDTs (DDT and its metabolites) in the tropical developing countries were apparently higher than those observed in the developed nations, suggesting extensive usage of these chemicals in the lower latitudes. CHLs (chlordane compounds) and PCBs (polychlorinated biphenyls) were also occasionally observed at higher levels in the tropics, implying that their usage area is also expanding southward. Distribution patterns of organochlorines in sediments showed smaller spatial variations on global terms, indicating that the chemicals released in the tropical environment are dispersed rapidly through air and water and retained less in sediments. The ratios of organochlorine concentrations in sediment and water phases were positively correlated with the latitude of sampling, suggesting that persistent and semivolatile compounds discharged in the tropics tend to be redistributed on a global scale.

Butyltins in muscle and liver of fish collected from certain Asian and Oceanian countries

Concentrations of butyltin residues were determined in muscle tissue of fish collected from local markets and sea food shops in India, Bangladesh, Thailand, Indonesia, Vietnam, Taiwan, Australia, Papua New Guinea and the Solomon Islands. Contamination levels were determined in the Asia-Pacific region and human exposure was estimated. Similarly, corresponding liver samples of fish muscle collected in Australia, Papua New Guinea and the Solomon Islands were analyzed to obtain information on partitioning of butyltin compounds between muscle and liver tissues. Butyltin compounds were detected in most of the samples which suggested widespread contamination in Asia and Oceania. The concentrations of butyltin compounds were, on average, an order of magnitude higher in liver than in muscle. Residue concentration of Sigmabutyltin in liver was found to be correlated significantly (p < 0.02) with those in muscle. Intensive ship-scrapping activities, sewage disposal and antifouling paints are considered the major sources of butyltins in this region. Increased proportions of MBT over DBT and TBT in samples from most locations indicated degradation of TBT to MBT in fish tissues during storage at 4 degrees C in the dark over 1-2 years. The possibility that fish have been subject to increased exposure to MBT and that TBT degrades to MBT quite rapidly in tropical environments are also considered. Butyltin concentrations in fish from Asia and Oceania were lower than those reported for Japan, Canada and the USA. Although the number of samples analyzed from each country was small, it is tentatively suggested that intake of butyltins by humans via consumption of fish in these countries was < 25% of the tolerable daily intake of 250 ng kg bw(-1) day(-1). To our knowledge, this is the first study reporting on butyltin pollution in developing Asian countries.

High accumulation of toxic butyltins in marine mammals from Japanese coastal waters.

Organotins are one of the most toxic chemicals in the aquatic environment. While contamination and toxic effects of organotin compounds in lower trophic aquatic organisms have been well-documented, no investigation has focused so far on higher aquatic organisms like marine mammals. We attempted to analyze butyltin compounds (BTCs), including mono-(MBTs), di- (DBTs), and tributyltin compounds (TBTs), in various tissues and organs of finless porpoise (Neophocaena phocaenoides) collected from Japanese coastal waters and detected these compounds in all the animals. The highest residue levels were found in the liver of a porpoise collected in the inland sea, recording more than 10 ppm BTCs on a wet weight basis. The composition of BTCs was different according to the tissues and organs with higher proportions of DBTs noticed in the liver and blood. Estimation of BTC burdens in tissues and organs indicated that muscle, liver, and blubber retained predominant portion of TBTs, DBTs, and MBTs. The occurrence of higher rates of TBTs on the whole implied the lower metabolic potential of porpoises to BTCs.

Persistent organochlorine residues in sediments from the Chukchi Sea, Bering Sea and Gulf of Alaska☆

Abstract Three surface sediments and two sediment cores were collected from the Gulf of Alaska, Bering Sea and Chukchi Sea, and analysed for persistent organochlorines (OCs). The geographical distributions of OCs showed different patterns according to their physicochemical properties. The concentrations of HCHs and HCB revealed rather uniform distribution, suggesting their more transportable nature in long-range atmospheric transport. On the other hand, DDTs and PCBs were predicted to be less transportable via the atmosphere due to the decreasing trends of residue levels in sediments from south to north. The OC profiles in the sediment core from the Gulf of Alaska which seemed to be preserved without turbation revealed the elevated residue levels from bottom to surface layers. This implies that the aerial inputs of OCs in the cold ocean are still continuing significantly. The accumulation rates of OCs into sediments were rather smaller than the atmospheric inputs, indicating that the residue levels in water bodies are unlikely to decrease rapidly in the near future.

Detection of butyltin compound residues in the blubber of marine mammals

Abstract The blubber samples of eight species (12 specimens) of marine mammals caught between 1981 and 1993 in seas surrounding Japan and in the Indian, North Pacific and Antarctic Oceans, were analysed for butyltin compounds (BTCs). The column chromatography using dry florisil and acetonitrile enabled isolation of BTCs from lipids in fatty tissues like blubber, and led to the reliable analysis with efficient recoveries for these contaminants. BTCs were detected in all the animals except a minke whale from the Antarctic Ocean. The highest residue levels were found in a finless porpoise from the Seto-inland Sea, Japan with a BTC concentration of 770 ng g −1 on wet wt basis. Geographical distribution of the BTC concentrations in marine mammals showed a decreasing trend from the coastal to the open seas, indicating the presence of larger pollution sources nearby the coastal regions. Compositions of the BTCs in the blubber of finless porpoises seemed to be different from those found in aquatic organisms of lower trophic levels. Lower contributions of dibutyltins to the total BTCs in the blubber suggest the presence of their specific metabolic pathways. To our knowledge, this is the first report on the detection of BTCs in marine mammals.

Concentrations of heavy metals, organochlorines, and organotins in horseshoe crab, Tachypleus tridentatus, from Japanese coastal waters

Concentrations of heavy metals, organochlorine pesticides, polychlorinated biphenyls and organotins were determined in horseshoe crabs, Tachypleus tridentatus, collected from Japanese coastal waters. Heavy metal concentrations were high in the hepatopancreas, gill and egg. Residue levels of heavy metals were comparable to those recorded in most benthic organisms from Japanese coastal waters. Organochlorine concentrations were detected at a few ng/g and the residue pattern followed the order of polychlorinated biphenyls (PCBs) > chlordane compounds (CHLs) > hexachlorocyclohexanes (HCHs) > dichlorodiphenyltrichloroethane (DDTs) > hexachlorobenzene (HCB). Butyltin concentrations were high in the hepatopancreas, ranging from 350–2,270 ng/g in Hakata Bay and 570–5,000 ng/g (on a wet wt basis) in Habu Bay. Elevated concentrations of butyltins were also detected in the eggs of horseshoe crabs. High accumulations of butyltins in horseshoe crabs may pose a serious threat to their survival and therefore needs immediate attention to prevent their extinction.

Fate of the insecticide HCH in the tropical coastal area of South India

Abstract The residue levels of the insecticide HCH in Vellar estuary, Tamil Nadu, South India were surveyed along with the physical structure of estuary and its hydrokinetic parameters to assess the transport of contaminants in tropical coastal areas. From the flux model it was estimated that most of the HCH applied to the catchment area of Vellar river is removed to the air and only a small part of it was drained to the sea. Compared to the present situation, the flux of HCH to the sea seems to be much larger in the past when the river structure was different from the present. This implies that at present the localized contamination of HCH in the sea is reducing: instead more rapid contamination is advancing on global terms due to the ‘long-range atmospheric transport’ of residues from the ‘point-source’ areas.

Genetic polymorphisms in glutathione S-transferase (GST) superfamily and arsenic metabolism in residents of the Red River Delta, Vietnam

To elucidate the role of genetic factors in arsenic metabolism, we investigated associations of genetic polymorphisms in the members of glutathione S-transferase (GST) superfamily with the arsenic concentrations in hair and urine, and urinary arsenic profile in residents in the Red River Delta, Vietnam. Genotyping was conducted for GST omega1 (GSTO1) Ala140Asp, Glu155del, Glu208Lys, Thr217Asn, and Ala236Val, GST omega2 (GSTO2) Asn142Asp, GST pi1 (GSTP1) Ile105Val, GST mu1 (GSTM1) wild/null, and GST theta1 (GSTT1) wild/null. There were no mutation alleles for GSTO1 Glu208Lys, Thr217Asn, and Ala236Val in this population. GSTO1 Glu155del hetero type showed higher urinary concentration of As(V) than the wild homo type. Higher percentage of DMA(V) in urine of GSTM1 wild type was observed compared with that of the null type. Strong correlations between GSTP1 Ile105Val and arsenic exposure level and profile were observed in this study. Especially, heterozygote of GSTP1 Ile105Val had a higher metabolic capacity from inorganic arsenic to monomethyl arsenic, while the opposite trend was observed for ability of metabolism from As(V) to As(III). Furthermore, other factors including sex, age, body mass index, arsenic level in drinking water, and genotypes of As (+3 oxidation state) methyltransferase (AS3MT) were also significantly co-associated with arsenic level and profile in the Vietnamese. To our knowledge, this is the first study indicating the associations of genetic factors of GST superfamily with arsenic metabolism in a Vietnamese population.

Genetic polymorphisms in AS3MT and arsenic metabolism in residents of the Red River Delta, Vietnam

To elucidate the role of genetic factors in arsenic (As) metabolism, we studied associations of single nucleotide polymorphisms (SNPs) in As (+3 oxidation state) methyltransferase (AS3MT) with the As concentrations in hair and urine, and urinary As profile in residents in the Red River Delta, Vietnam. Concentrations of total As in groundwater were 0.7-502 mug/l. Total As levels in groundwater drastically decreased by using sand filter, indicating that the filter could be effective to remove As from raw groundwater. Concentrations of inorganic As (IAs) in urine and total As in hair of males were higher than those of females. A significant positive correlation between monomethylarsonic acid (MMA)/IAs and age in females indicates that older females have higher methylation capacity from IAs to MMA. Body mass index negatively correlated with urinary As concentrations in males. Homozygote for SNPs 4602AA, 35991GG, and 37853GG, which showed strong linkage disequilibrium (LD), had higher percentage (%) of dimethylarsinic acid (DMA) in urine. SNPs 4740 and 12590 had strong LD and associated with urinary %DMA. Although SNPs 6144, 12390, 14215, and 35587 comprised LD cluster, homozygotes in SNPs 12390GG and 35587CC had lower DMA/MMA in urine, suggesting low methylation capacity from MMA to DMA in homo types for these SNPs. SNPs 5913 and 8973 correlated with %MMA and %DMA, respectively. Heterozygote for SNP 14458TC had higher MMA/IAs in urine than TT homozygote, indicating that the heterozygote may have stronger methylation ability of IAs. To our knowledge, this is the first study on the association of genetic factors with As metabolism in Vietnamese.